JP4024942B2 - Dye-sensitized photochemical cell - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、光化学電池に係り、特に表面に色素を担持した半導体電極を用いる色素増感型光化学電池に関する。
【０００２】
【従来の技術】
一般に、透明半導体層表面に色素を担持させてなる電極を用いた光化学電池には、例えば、特開平１−２２０３８０号公報または特表平５−５０４０２３号公報に記載されているように微粒子状の金属酸化物を焼結することにより得られる微細構造をもつ半導体電極が用いられる。
【０００３】
すなわち、光化学電池に用いられてきた半導体電極の製造に当たっては、例えば酸化チタン膜の場合、まず、チタニウムイソプロポキシドなどの有機チタン化合物を含む溶媒に電極を浸漬し、引き上げた後、電極を焼結して半導体膜を得る。次いで、得られた半導体膜表面に色素を吸着させた後、液状のキャリア移動層を介して対向電極で挟み込むことにより湿式光化学電池が得られる。
【０００４】
最近では、広い波長範囲の光を有効に光電変換して、高い光電変換効率を得ることが望まれている。
【０００５】
【発明が解決しようとする課題】
本発明は、広い波長範囲の光を高い変換効率で光電変換し得る色素増幅型光化学電池を提供することを目的とする。
【０００６】
【課題を解決するための手段】
上記課題を解決するために、本発明は、光の透過方向に積層された２つ以上の光化学電池ユニットを具備し、前記光化学電池ユニットは、入射側に設けられた色素増感透明半導体電極、前記色素増感透明半導体電極に離間して配置され、透明導電性層からなる対向電極、および、前記色素増感透明半導体電極と前記対向電極とに挟持されたキャリア移動層を有し、前記色素増感透明半導体電極は、透明基板上に設けられた透明電極、この透明電極上に形成された透明半導体層および、この透明半導体層に吸着されるとともに前記キャリア移動層に接触する増感色素により構成され、各光化学電池ユニットの色素増感透明半導体電極に含まれる増感色素の吸収波長が異なることを特徴とする色素増感型透明半導体電池を提供する。
【０００７】
以下、本発明の色素増感型透明半導体電池を詳細に説明する。
【０００８】
従来の単一層の増感色素を用いた光化学電池では、その増感色素の吸収波長より長波長の光は吸収せず、より広い波長領域を吸収するためにより長波長側に吸収波長をもたせた場合には、それだけ低エネルギーの光しか取り出せない。したがって、光電変換効率を高めるには限界があった。
【０００９】
本発明においては、増感色素以外の全ての部材、すなわち透明電極、透明半導体層、キャリア移動層および対向電極を、透明な部材で構成することにより光化学電池ユニットを作製し、異なる吸収波長の増感色素を含んだ２つ以上の光化学電池ユニットを光入射方向に対して重ねることによって、積層型光化学電池を得た。かかる構成としたことにより、入射光中の各波長の光をそれぞれの増感色素に吸着させ、効率よく光電変換することが可能となった。
【００１０】
図１には、本発明の光化学電池の一例の構成を表す断面図を示す。
【００１１】
図示する光化学電池７０は、第１の光化学電池ユニット７８と第２の光化学電池ユニット８８とが光透過方向に積層された構造である。第１の光化学電池ユニット７８は、第１の色素増感透明半導体電極７５および第１の対向電極７６と、これらの電極に挟持された第１のキャリア移動層７７とを有し、第２の光化学電池ユニット８８は、第２の色素増感透明半導体電極８５、および透明基板８９に形成された第２の対向電極８６とを有している。各光化学電池ユニットにおいては、色素増感透明半導体電極が入射側となるように配置される。
【００１２】
第１の光化学電池ユニット７８における第１の色素増感透明半導体電極７５は、透明基板７１上に形成された透明電極７２および透明半導体層７３と、この透明半導体層に吸着した第１の増感色素７４により構成され、第２の光化学電池ユニット８８における第２の色素増感透明半導体電極８５もまた、透明基板８１上に形成された透明電極８２および透明半導体層８３と、この透明半導体層に吸着した第２の増感色素８４により構成されている。
【００１３】
本発明の光化学電池を構成するための透明電極、透明半導体、キャリア移動層および対向電極としては、次のようなものを用いることができる。
【００１４】
透明電極に用いられる材料としては、可視光領域の吸収が少なく、導電性のフッ素やインジウム、アルミニウムなどをドープした酸化スズ、酸化亜鉛などが好ましい。
【００１５】
半導体層として使用し得る材料は、ｎ型ｐ型ともに可視光領域の吸収が少ない半導体で、金属酸化物半導体では遷移金属の酸化物、遷移金属の酸化物、例えば、チタン、ジルコニウム、ハフニウム、ストロンチウム、亜鉛、インジウム、イットリウム、ランタン、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステンの酸化物、およびこれらの酸化物が好ましい。ＳｒＴｉＯ3、ＣａＴｉＯ3、ＢａＴｉＯ3、ＭｇＴｉＯ3、ＳｒＮｂ2Ｏ6のようなペロブスカイト、あるいはこれらの複合酸化物または酸化物混合物、ＧａＮなどが好ましい。特に透明ｐ型半導体層としては、ＣｕＡｌＯ2などが好ましい。
【００１６】
透明半導体層には増感色素が吸着される。増感色素としては、ルテニウム−トリス、ルテニウム−ビス、オスミウム−トリス、オスミウム−ビス型の遷移金属錯体、またはルテニウム−シス−ジアクア−ビピリジル錯体、または各種金属フタロシアニン、ペリレンテトラカルボン酸、ポルフィリン、またはペリレンやコロネンなど多環芳香族化合物、またはテトラチアフルバレンやテトラシアノキノジメタンなど電荷移動錯体材料であることが好ましい。
【００１７】
キャリア移動層としては、液体イオン移動層、固体イオン移動層、固体ホールもしくは電子移動層が用いられる。液体イオン移動層としては、ヨウ化物、臭化物、ヒドロキノンなどのイオンキャリアを含むアセトニトリルやエチレンカーボネートもしくはその混合液が好ましい。
【００１８】
対向電極は、例えばフッ素ドープされた酸化スズにより形成することができる。
【００１９】
ただし、本発明の光化学電池においては、各光化学電池ユニットの色素増感透明半導体電極に含まれる増感色素の吸収波長は、それぞれ異なっていることが必要である。すなわち、第１の光化学電池ユニット７８を構成する第１の色素増感透明半導体電極７５に含まれる第１の増感色素７４と、第２の光化学電池ユニット８８を構成する第２の色素増感透明半導体電極８５に含まれる第２の増感色素８４とは、吸収波長が異なっている。
【００２０】
また、本発明の光化学電池において、広い波長範囲の光を高い変換効率で光電変換するためには、光の入射方向に遠い層の増感色素ほど吸収波長を長波長側にもたせることが好ましい。例えば、第１の光化学ユニット７８側から光を入射する場合、入射方向側の増感色素７４は、光源から遠くに設けられた増感色素８４より短波長の光を吸収して、それより長波長の光を下の層に透過することが好ましい。
【００２１】
第２の光化学電池ユニットの上に第３の光化学電池ユニットさらに積層して３層構造とする場合も、前述と同様に、第２の光化学電池ユニットにおける増感色素は、第１層の増感色素の次に短波長の光を吸収して、それより長波長の光を第３の光化学電池ユニット層に透過するように増感色素を選択する。
【００２２】
なお、吸収係数が互いに１０5ｃｍ-1以上の波長領域をもたない複数の増感色素を用いる場合には、吸収波長に応じて増感色素の積層順を決定することは必ずしも必要ではない。こうした増感色素を用いる場合には、各層を重ねる順番は、前述した光の入射方向から遠い層の増感色素ほど吸収波長を長波長にもたせるという規則に従わずに重ねても、各層の増感色素は効率的に光を吸収することができる。
【００２３】
２種類の増感色素を用いた構造より、３種類の増感色素を用いたほうが好ましく、より多くの種類の増感色素を用いたより多くの光化学電池ユニットを積層した構造とすることによって、より広い波長範囲の光を吸収できるので高い光電変換効率が得られる。
【００２４】
このようなそれぞれ異なる吸収スペクトルの増感色素をもつ光化学電池ユニットを重ねる場合、各層の開放端電圧と短絡電流はそれぞれ異なるため、高い開放端電圧のためには各電池を直列に、高い短絡電流のためには各層を並列に接続する。
【００２５】
本発明において、異なる吸収波長を有する複数の増感色素をそれぞれ含有する複数の光化学電池ユニットを光透過方向に積層することにより光化学電池を構成しているので、広い波長範囲の光を高い変換効率で光電変換することが可能となった。
【００２６】
【発明の実施の形態】
以下、具体例を示して本発明をさらに詳細に説明する。
【００２７】
（実施例６）
まず、第１の増感色素（ルテニウム錯体）が担持された色素増感透明半導体電極を作製して、第１の色素増感透明半導体電極を得た。具体的には、粒子径１５ｎｍのＴｉＯ2微粒子を水に懸濁させて懸濁液を調製し、この懸濁液を、フッ素ドープした酸化スズ透明電極上に塗布した。その後、４５０℃で焼成して透明半導体層としてのＴｉＯ2膜を形成した。このＴｉＯ2膜は、膜厚１０μｍであり、ラフネスファクターは１０００であった。得られたＴｉＯ2膜を増感色素としてのシス−ビス（イソチオシアナート）ビス（２，２’ビピリジル−４，４’−ジカルボキシレート）ルテニウムのエタノール溶液中に浸漬させ、溶液の沸点温度にて３０分間加熱還流することにより第１の色素増感透明半導体電極を得た。
【００２８】
また、増感色素をペリレンジイミドに変更した以外は、同様の手順で第２の色素増感透明半導体電極を作製した。この第２の色素増感透明半導体電極の裏面には、フッ素ドープされた酸化スズにより透明電極を形成して第１の対向電極を設けた。
【００２９】
一方、（Ｃ3Ｈ7）4ＮＩおよびＩ2を等量ずつ含むアセトニトリルとエチレンカーボネートとを体積比率にしてそれぞれ２０％および８０％混合して、電解液を調製した。この電解液を、空孔率５０％膜厚１０μｍのポリオレフィン微多孔質セパレーターとともに、前述の第１および第２の色素増感透明半導体電極で挟み込んで第１のキャリア移動層を形成した。さらに、第２の対向電極としてのＩＴＯ電極が形成されたガラス基板と第２の色素増感透明半導体電極とで、前述と同様の電解液等を挟み込んで第２のキャリア移動層を形成し、これらの側面を樹脂で封入した。次いで、リード線を設けて図１に示すような２層型光化学電池を得た。
【００３０】
ここで用いた第１および第２の増感色素の吸収スペクトルを、図２のグラフに示す。図２のグラフ中、曲線ｅは、第１の色素増感透明半導体電極に担持された第１の増感色素であるルテニウム錯体の吸収スペクトルを表し、曲線ｆは、第２の色素増感透明半導体電極に担持された第２の増感色素であるペリレンジイミドの吸収スペクトルを表す。
【００３１】
（実施例７）
第１の増感色素としてアントラキノン系イエロー色素を用いた以外は、前述の実施例６と同様にして第１の色素増感透明半導体電極を作製し、第２の増感色素としてアントラキノン系マゼンタ色素を用いた以外は、前述の実施例６と同様にして第２の色素増感透明半導体電極を作製した。さらに、第３の増感色素としてアントラキノン系シアン色素を用いた以外は、第２の色素増感透明半導体電極と同様にして第３の色素増感透明半導体電極を得た。
【００３２】
第１の色素増感透明半導体電極と第２の色素増感透明半導体層との間、および第２の色素増感透明半導体電極と第３の色素増感透明半導体電極との間には、前述の実施例６の場合と同様にしてそれぞれ第１および第２のキャリア移動層を形成した。さらに、第３の対向電極としてのＩＴＯ電極が形成されたガラス基板と第３の色素増感透明半導体電極とで、前述と同様の電解液等を挟み込んで第３のキャリア移動層を形成し、これらの側面を樹脂で封入した。次いで、リード線を設けて図３に示すような３層型光化学電池を得た。
【００３３】
図示する光化学電池１００は、第２の光化学電池ユニット８８上に第３の光化学電池ユニット９８が積層されている以外は、図１に示したものと同様の構成である。すなわち、第３の光化学電池ユニット９８においては、透明基板９１、透明電極９２、透明半導体層９３および増感色素９４からなる第３の色素増感透明半導体電極９５と、ガラス基板９９に形成された第３の対向電極９７とにより第３のキャリア移動層９６が挟持されている。
【００３４】
本実施例においては、第１の増感色素７４としてアントラキノン系イエロー色素を用い、第２の増感色素としてアントラキノン系マゼンタ色素を用い、第３の増感色素としてアントラキノン系シアン色素を用いている。これらの増感色素の吸収スペクトルを図４のグラフに示す。図４のグラフ中、曲線ｇはアントラキノン系イエロー色素の吸収スペクトルを表し、曲線ｈはアントラキノン系マゼンタ色素の吸収スペクトルを表し、曲線ｉはアントラキノン系シアン色素の吸収スペクトルを表す。
【００３５】
（実施例８）
第１の増感色素としてアントラキノン系シアン色素を用い、第３の増感色素としてアントラキノン系イエロー色素を用いた以外は、前述の実施例７と同様の手順で３層型光化学電池を得た。
【００３６】
図４のグラフに示したように、アントラキノン系イエロー色素の吸収スペクトル、アントラキノン系マゼンタ色素の吸収スペクトル、およびアントラキノン系シアン色素の吸収スペクトルは、それぞれ独立したピークを有しており、しかも１０5ｃｍ-1の重なりをもたないので、増感色素層の順番を変更することができる。
【００３７】
（比較例１）
前述の実施例６と同様の手順で色素増感型透明半導体電極を作製し、ＩＴＯ基板表面に白金を蒸着して対向電極を作製した。
【００３８】
こうして得られた色素増感透明半導体電極と対向電極とで、前述の実施例６と同様の組成の電解液および微多孔質セパレーターを挟み込み、これらの側面を樹脂で封入した後、リード線を取り付けて本比較例の光化学電池を得た。
【００３９】
実施例６ないし８および比較例１の各々の光化学電池について、ワコム社製疑似太陽光源を用いて、７５０ｍＷ／ｃｍ2の光量で光照射を行い、その開放端電圧および光電変換効率をケースレー社のソースメジャーユニット２３６により計測した。実施例６〜８の光化学電池については、開放端電圧も測定した。
【００４０】
実施例６〜８の光化学電池と、比較例１の光化学電池の開放端電圧、短絡電流を、光電変換効率とともに下記表１にまとめる。
【００４１】
【表１】
【００４２】
【発明の効果】
以上説明したように、本発明によれば、広い波長範囲の光を高い変換効率で光電変換し得る色素増幅型光化学電池が提供される。
【００４３】
本発明の色素増感型光化学電池は、入射光エネルギーを有効に光電変換することができ、その工業的価値は絶大である。
【図面の簡単な説明】
【図１】本発明の色素増感型光化学電池の一例の構成を表す断面図。
【図２】実施例６の積層増感型光化学電池に用いた２種類の増感色素の吸収波長と、その吸光度の関係とを表すグラフ図。
【図３】本発明の色素増感型光化学電池の他の例の構成を表す断面図。
【図４】実施例７の積層増感型光化学電池に用いた３種類の増感色素の吸収波長と吸光度の関係とを表すグラフ図。
【符号の説明】
７０…光化学電池； ７１，８１，９１…透明基板
７２，８２，９２…透明電極； ７３，８３，９３…透明半導体層
７４，８４，９４…増感色素； ７５，８５，９５…色素増感透明半導体電極
７６，８６，９６…対向電極； ７７，８７，９７…キャリア移動層
７８，８８，９８…光化学電池ユニット； ８９，９９…ガラス基板
１００…光化学電池。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photochemical cell, and more particularly to a dye-sensitized photochemical cell using a semiconductor electrode carrying a dye on its surface.
[0002]
[Prior art]
In general, in a photochemical battery using an electrode in which a pigment is supported on the surface of a transparent semiconductor layer, for example, as described in JP-A-1-220380 or JP-T-5-504023, A semiconductor electrode having a microstructure obtained by sintering a metal oxide is used.
[0003]
That is, in the production of a semiconductor electrode that has been used for a photochemical battery, for example, in the case of a titanium oxide film, first, the electrode is immersed in a solvent containing an organic titanium compound such as titanium isopropoxide, pulled up, and then fired. As a result, a semiconductor film is obtained. Next, after a dye is adsorbed on the surface of the obtained semiconductor film, a wet photochemical battery is obtained by sandwiching it with a counter electrode through a liquid carrier moving layer.
[0004]
Recently, it has been desired to effectively photoelectrically convert light in a wide wavelength range to obtain high photoelectric conversion efficiency.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a dye amplification type photochemical cell capable of photoelectrically converting light in a wide wavelength range with high conversion efficiency.
[0006]
[Means for Solving the Problems]
In order to solve the above problems, the present invention comprises two or more photochemical battery units stacked in the light transmission direction, the photochemical battery unit comprising a dye-sensitized transparent semiconductor electrode provided on the incident side, A dye-sensitized transparent semiconductor electrode, and a counter electrode made of a transparent conductive layer, and a carrier moving layer sandwiched between the dye-sensitized transparent semiconductor electrode and the counter electrode; The sensitized transparent semiconductor electrode comprises a transparent electrode provided on a transparent substrate, a transparent semiconductor layer formed on the transparent electrode, and a sensitizing dye adsorbed on the transparent semiconductor layer and in contact with the carrier moving layer. Provided is a dye-sensitized transparent semiconductor battery that is configured and has different absorption wavelengths of sensitizing dyes contained in the dye-sensitized transparent semiconductor electrode of each photochemical battery unit.
[0007]
Hereinafter, the dye-sensitized transparent semiconductor battery of the present invention will be described in detail.
[0008]
In conventional photochemical cells using a single-layer sensitizing dye, light longer than the absorption wavelength of the sensitizing dye is not absorbed, and an absorption wavelength is provided on the longer wavelength side in order to absorb a wider wavelength region. In some cases, only low energy light can be extracted. Therefore, there is a limit to increasing the photoelectric conversion efficiency.
[0009]
In the present invention, a photochemical battery unit is prepared by constituting all members other than the sensitizing dye, that is, the transparent electrode, the transparent semiconductor layer, the carrier moving layer, and the counter electrode, with a transparent member, and increasing the different absorption wavelengths. Two or more photochemical battery units containing dyes were stacked in the light incident direction to obtain a stacked photochemical battery. By adopting such a configuration, light of each wavelength in incident light can be adsorbed to each sensitizing dye, and photoelectric conversion can be efficiently performed.
[0010]
In FIG. 1, sectional drawing showing the structure of an example of the photochemical battery of this invention is shown.
[0011]
The illustrated
[0012]
The first dye-sensitized
[0013]
The following can be used as a transparent electrode, a transparent semiconductor, a carrier moving layer, and a counter electrode for constituting the photochemical battery of the present invention.
[0014]
As a material used for the transparent electrode, tin oxide, zinc oxide or the like doped with conductive fluorine, indium, aluminum or the like is preferable because it absorbs less in the visible light region.
[0015]
The material that can be used for the semiconductor layer is a semiconductor that has low absorption in the visible light region in both the n-type and p-type. In the case of a metal oxide semiconductor, an oxide of a transition metal, an oxide of a transition metal, such as titanium, zirconium, hafnium, strontium Zinc, indium, yttrium, lanthanum, vanadium, niobium, tantalum, chromium, molybdenum, tungsten oxides, and oxides thereof are preferable. A perovskite such as SrTiO 3 , CaTiO 3 , BaTiO 3 , MgTiO 3 , SrNb 2 O 6 , or a composite oxide or oxide mixture thereof, GaN, or the like is preferable. In particular, CuAlO 2 or the like is preferable as the transparent p-type semiconductor layer.
[0016]
A sensitizing dye is adsorbed on the transparent semiconductor layer. Sensitizing dyes include ruthenium-tris, ruthenium-bis, osmium-tris, osmium-bis type transition metal complexes, or ruthenium-cis-diaqua-bipyridyl complexes, or various metal phthalocyanines, perylenetetracarboxylic acids, porphyrins, or A polycyclic aromatic compound such as perylene or coronene, or a charge transfer complex material such as tetrathiafulvalene or tetracyanoquinodimethane is preferable.
[0017]
As the carrier transfer layer, a liquid ion transfer layer, a solid ion transfer layer, a solid hole, or an electron transfer layer is used. As the liquid ion transfer layer, acetonitrile, ethylene carbonate or a mixture thereof containing an ion carrier such as iodide, bromide, hydroquinone or the like is preferable.
[0018]
The counter electrode can be made of, for example, fluorine-doped tin oxide.
[0019]
However, in the photochemical battery of the present invention, the absorption wavelengths of the sensitizing dyes contained in the dye-sensitized transparent semiconductor electrode of each photochemical battery unit must be different from each other. That is, the first dye
[0020]
Moreover, in the photochemical cell of the present invention, in order to photoelectrically convert light in a wide wavelength range with high conversion efficiency, it is preferable that the sensitizing dye in a layer farther in the light incident direction has an absorption wavelength on the longer wavelength side. For example, when light is incident from the first
[0021]
Even when the third photochemical battery unit is further laminated on the second photochemical battery unit to form a three-layer structure, the sensitizing dye in the second photochemical battery unit is sensitized in the first layer as described above. A sensitizing dye is selected so as to absorb light having a shorter wavelength next to the dye and transmit light having a longer wavelength to the third photochemical battery unit layer.
[0022]
In addition, when using a plurality of sensitizing dyes whose absorption coefficients do not have a wavelength region of 10 5 cm −1 or more, it is not always necessary to determine the stacking order of the sensitizing dyes according to the absorption wavelength. . When such a sensitizing dye is used, the order in which the layers are stacked is not limited to the above-described rule that the absorption wavelength of the sensitizing dye in the layer farther from the light incident direction is set to a longer wavelength. The dye is capable of absorbing light efficiently.
[0023]
It is more preferable to use three types of sensitizing dyes than a structure using two types of sensitizing dyes. By making a structure in which more photochemical battery units using more types of sensitizing dyes are laminated, High photoelectric conversion efficiency can be obtained because light in a wide wavelength range can be absorbed.
[0024]
When stacking photochemical battery units with sensitizing dyes having different absorption spectra, the open-circuit voltage and short-circuit current of each layer are different. For this purpose, the layers are connected in parallel.
[0025]
In the present invention, since a photochemical cell is configured by laminating a plurality of photochemical cell units each containing a plurality of sensitizing dyes having different absorption wavelengths in the light transmission direction, light having a wide wavelength range has high conversion efficiency. It became possible to perform photoelectric conversion.
[0026]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to specific examples.
[0027]
(Example 6)
First, a dye-sensitized transparent semiconductor electrode carrying a first sensitizing dye (ruthenium complex) was produced to obtain a first dye-sensitized transparent semiconductor electrode. Specifically, TiO 2 fine particles having a particle diameter of 15 nm were suspended in water to prepare a suspension, and this suspension was applied onto a fluorine-doped tin oxide transparent electrode. Then, to form a TiO 2 film as the transparent semiconductor layer and baked at 450 ° C.. This TiO 2 film had a thickness of 10 μm and a roughness factor of 1000. The obtained TiO 2 film was immersed in an ethanol solution of cis-bis (isothiocyanate) bis (2,2′bipyridyl-4,4′-dicarboxylate) ruthenium as a sensitizing dye, and the boiling temperature of the solution The first dye-sensitized transparent semiconductor electrode was obtained by heating at reflux for 30 minutes.
[0028]
Moreover, the 2nd dye-sensitized transparent semiconductor electrode was produced in the same procedure except having changed the sensitizing dye into perylene diimide. On the back surface of the second dye-sensitized transparent semiconductor electrode, a transparent electrode was formed from fluorine-doped tin oxide to provide a first counter electrode.
[0029]
On the other hand, acetonitrile and ethylene carbonate containing equal amounts of (C 3 H 7 ) 4 NI and I 2 were mixed at a volume ratio of 20% and 80%, respectively, to prepare an electrolytic solution. This electrolyte solution was sandwiched between the above-described first and second dye-sensitized transparent semiconductor electrodes together with a polyolefin microporous separator having a porosity of 50% and a film thickness of 10 μm to form a first carrier transfer layer. Further, a second carrier transport layer is formed by sandwiching an electrolyte solution similar to the above between the glass substrate on which the ITO electrode as the second counter electrode is formed and the second dye-sensitized transparent semiconductor electrode, These side surfaces were encapsulated with resin. Next, lead wires were provided to obtain a two-layer photochemical battery as shown in FIG.
[0030]
The absorption spectra of the first and second sensitizing dyes used here are shown in the graph of FIG. In the graph of FIG. 2, the curve e represents the absorption spectrum of the ruthenium complex, which is the first sensitizing dye supported on the first dye-sensitized transparent semiconductor electrode, and the curve f represents the second dye-sensitized transparent film. 2 represents an absorption spectrum of perylene diimide as a second sensitizing dye supported on a semiconductor electrode.
[0031]
(Example 7)
A first dye-sensitized transparent semiconductor electrode was prepared in the same manner as in Example 6 except that an anthraquinone yellow dye was used as the first sensitizing dye, and an anthraquinone magenta dye was used as the second sensitizing dye. A second dye-sensitized transparent semiconductor electrode was produced in the same manner as in Example 6 except that was used. Furthermore, a third dye-sensitized transparent semiconductor electrode was obtained in the same manner as the second dye-sensitized transparent semiconductor electrode, except that an anthraquinone cyan dye was used as the third sensitizing dye.
[0032]
Between the first dye-sensitized transparent semiconductor electrode and the second dye-sensitized transparent semiconductor layer and between the second dye-sensitized transparent semiconductor electrode and the third dye-sensitized transparent semiconductor electrode, The first and second carrier transport layers were formed in the same manner as in Example 6. Further, a third carrier moving layer is formed by sandwiching an electrolyte solution similar to the above between the glass substrate on which the ITO electrode as the third counter electrode is formed and the third dye-sensitized transparent semiconductor electrode, These side surfaces were encapsulated with resin. Next, lead wires were provided to obtain a three-layer photochemical battery as shown in FIG.
[0033]
The illustrated
[0034]
In this embodiment, an anthraquinone yellow dye is used as the first sensitizing
[0035]
(Example 8)
A three-layer photochemical cell was obtained in the same manner as in Example 7 except that an anthraquinone cyan dye was used as the first sensitizing dye and an anthraquinone yellow dye was used as the third sensitizing dye.
[0036]
As shown in the graph of FIG. 4, the absorption spectrum of the anthraquinone yellow dye, the absorption spectrum of the anthraquinone magenta dye, and the absorption spectrum of the anthraquinone cyan dye have independent peaks, and are 10 5 cm. Since there is no -1 overlap, the order of the sensitizing dye layers can be changed.
[0037]
(Comparative Example 1)
A dye-sensitized transparent semiconductor electrode was prepared in the same procedure as in Example 6 described above, and platinum was deposited on the ITO substrate surface to prepare a counter electrode.
[0038]
The dye-sensitized transparent semiconductor electrode and the counter electrode thus obtained are sandwiched between an electrolyte solution and a microporous separator having the same composition as in Example 6 described above, and these side surfaces are sealed with resin, and then lead wires are attached. Thus, a photochemical battery of this comparative example was obtained.
[0039]
For each of the photochemical batteries of Examples 6 to 8 and Comparative Example 1, light irradiation was performed with a light amount of 750 mW / cm 2 using a simulated solar light source manufactured by Wacom, and the open-end voltage and photoelectric conversion efficiency were measured by Keithley. Measurement was performed by the source measure unit 236. About the photochemical battery of Examples 6-8, the open end voltage was also measured.
[0040]
The open circuit voltage and the short circuit current of the photochemical batteries of Examples 6 to 8 and the photochemical battery of Comparative Example 1 are summarized in Table 1 below together with the photoelectric conversion efficiency.
[0041]
[Table 1]
[0042]
【The invention's effect】
As described above, according to the present invention, a dye amplification type photochemical cell capable of photoelectrically converting light in a wide wavelength range with high conversion efficiency is provided.
[0043]
The dye-sensitized photochemical cell of the present invention can effectively photoelectrically convert incident light energy, and its industrial value is tremendous.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing the structure of an example of a dye-sensitized photochemical cell of the present invention.
2 is a graph showing the absorption wavelength of two types of sensitizing dyes used in the laminated sensitized photochemical battery of Example 6 and the relationship between the absorbances thereof. FIG.
FIG. 3 is a cross-sectional view showing the structure of another example of the dye-sensitized photochemical cell of the present invention.
4 is a graph showing the relationship between the absorption wavelength and absorbance of three types of sensitizing dyes used in the laminated sensitized photochemical battery of Example 7. FIG.
[Explanation of symbols]
70 ... Photochemical battery; 71, 81, 91 ...
Claims (4)
前記光化学電池ユニットは、入射側に設けられた色素増感透明半導体電極、前記色素増感透明半導体電極に離間して配置され、透明導電性層からなる対向電極、および、前記色素増感透明半導体電極と前記対向電極とに挟持されたキャリア移動層を有し、
前記色素増感透明半導体電極は、透明基板上に設けられた透明電極、この透明電極上に形成された透明半導体層および、この透明半導体層に吸着されるとともに前記キャリア移動層に接触する増感色素により構成され、
各光化学電池ユニットの色素増感透明半導体電極に含まれる増感色素の吸収波長が異なることを特徴とする色素増感型透明半導体電池。Comprising two or more photochemical battery units stacked in the light transmission direction;
The photochemical battery unit includes a dye-sensitized transparent semiconductor electrode provided on the incident side, a counter electrode made of a transparent conductive layer and spaced apart from the dye-sensitized transparent semiconductor electrode, and the dye-sensitized transparent semiconductor A carrier moving layer sandwiched between an electrode and the counter electrode;
The dye-sensitized transparent semiconductor electrode includes a transparent electrode provided on a transparent substrate, a transparent semiconductor layer formed on the transparent electrode, and a sensitization that is adsorbed to the transparent semiconductor layer and contacts the carrier moving layer. Composed of pigments,
A dye-sensitized transparent semiconductor battery, wherein the absorption wavelength of the sensitizing dye contained in the dye-sensitized transparent semiconductor electrode of each photochemical battery unit is different.
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